Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
  • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
  • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
  • C08G18/4219—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from aromatic dicarboxylic acids and dialcohols in combination with polycarboxylic acids and/or polyhydroxy compounds which are at least trifunctional
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
  • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
  • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
  • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
  • C08G18/4252—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids derived from polyols containing polyether groups and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
  • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
  • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
  • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
  • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2170/00—Compositions for adhesives
  • C08G2170/80—Compositions for aqueous adhesives

Definitions

• Water-dispersible polyurethanes contain compounds with hydrophilic groups, which ensure dispersibility.
• Compounds with hydrophilic groups are in particular also those with carboxylic acid groups and at least one group which is reactive toward isocyanate, i.e. at least one primary or secondary amino or a hydroxyl group used.
• EP-A-18 665 discloses, in the case of polyurethanes which have been modified with polyols based on fatty acid esters, to avoid side reactions, reaction products from sterically hindered diols having a maximum of 18 carbon atoms and monoanhydrides of polycarboxylic acids with at least 3 carboxyl groups as hydrophilic compounds to use.
• DE-B-1 237 306 describes the reaction of polyurethane prepolymers with cyclic compounds which have groups capable of salt formation after ring opening.
• reaction products of polyols and dicarboxylic acid anhydrides can be used as hydrophilic compounds.
• EP-A-171 relates to a process for the preparation of polyurethanes containing carboxylate and amide groups.
• tri- or tetracarboxylic acid monoanhydrides are reacted with polyols and the carboxyl groups still present are partly neutralized and partly reacted with isocyanate compounds to form amides.
• Dihydroxyl compounds as reaction products of tetracarboxylic acid dianhydrides with diols are not known from this document.
• polyurethanes which have been hydrophilically modified with compounds containing carboxylic acid groups to date have unsatisfactory water resistance, in particular considerable water swellability.
• the object of the present invention was to remedy this disadvantage.
• Aliphatic, cycloaliphatic and aromatic diisocyanates are particularly suitable as polyisocyanates (a).
• Those having the general formula X (NCO) 2 are preferably used, where X represents an aliphatic hydrocarbon radical having 4 to 12 C atoms, a cycloaliphatic radical having 6 to 15 atoms or an aromatic hydrocarbon radical having 7 to 15 C atoms.
• Suitable aliphatic, cycloaliphatic and aromatic diisocyanates are e.g. B. 1,4-butane diisocyanate, 1,6-hexane diisocyanate, 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, 4,4'-diisocyanatodiphenylmethane, 4,4'-diisocyanatodicydohexylmethane, 2 , 4- and 2,6-toluenediisocyanate.
• Mixtures of the diisocyanates can also be used. Mixtures of aliphatic or cycloaliphatic diisocyanates with aromatic diisocyanates in a molar ratio of 1: 4 to 5: 1 have proven to be suitable.
• Suitable polyhydroxyl compounds (c) are in particular dihydroxyl compounds with a molecular weight above 500 to 5000, e.g. the known polyesters, polyethers, polythioethers, polylactones, polyacetals, polycarbonates and polyesteramides with 2 hydroxyl groups. Those dihydroxyl compounds whose molecular weight is between 750 and 3000 are preferred. Mixtures of these dihydroxyl compounds can of course also be used.
• Suitable dihydroxyl compounds b) have a molecular weight between 500 and 10,000, in particular 800 and 8,000, particularly preferably between 800 and 5,000 g / mol. They can be obtained by reacting the above-mentioned dihydroxyl compounds with tetracarboxylic dianhydrides in a molar ratio nis from 2: 1 to 1.05, preferably from 2: 1 to 1.5: 1. During the reaction, the tetracarboxylic diester is formed by opening the anhydride rings. There is essentially no reaction of the two remaining carboxylic acid groups with the dihydroxyl compounds to the tri- or tetraesters.
• the reaction between the dihydroxyl compound and the tetracarboxylic dianhydride is preferably carried out at temperatures between 70 and 150 ° C, particularly preferably between 90 and 13 0 ° C in the melt or an inert solvent.
• the end of the reaction can be determined by the fact that no anhydride band can be seen, for example, in the infrared spectrum.
• a solvent such.
• Compounds d) are those with at least one isocyanate-reactive group, i.e. a hydroxyl or a primary or secondary amino group, and an anionic or convertible group.
• B. aminocarboxylic acids or aminosulfonic acids e.g. B. lysine, ß-alanine, N- (2-aminoethyl) -2-aminoethanesulfonic acid and the adducts mentioned in DE-A-20 34 479 of aliphatic diprimeric diamines with a-olefinic carboxylic acids, for. B. the adduct of ethylenediamine with acrylic acid.
• Dihydroxycarboxylic acids in particular dihydroxyalkylcarboxylic acids having 3 to 10 carbon atoms, are preferably used. May be mentioned for. B. 2,2-Dimethylolpropionic acid.
• inorganic and / or organic bases such as e.g. Sodium hydroxide, potassium hydroxide, ammonia or tertiary amines, e.g. B. triethylamine or dimethylaminopropanol can be used.
• alkaline earth metal hydroxides e.g. B. Ca (OH) 2 or Ba- (OH) 2 in admixture with the above-mentioned inorganic or organic bases.
• the potentially anionic groups can be neutralized before or during the dispersion of the polyurethane in water.
• emulsifying components e.g. monohydric polyether alcohols with a molecular weight in the range from 500 to 10,000 g / mol, preferably from 1,000 to 5,000 g / mol.
• emulsifiers is generally not necessary due to the content of structural components b) and, if appropriate, d).
• Build-up components (e) are customary chain extenders, ie essentially compounds which contain two hydroxyl groups, two primary or secondary amino groups or one hydroxyl and one primary or secondary amino group.
• dihydroxyl compounds such as propanediol- (1,3), butanediol- (1,4), diamines such as ethylenediamine, hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (Isophoronediamine), 4,4'-diaminodicyclohexylmethane, 2,4-diamino-cyclohexane, 1,2-diamino-propane, hydrazine or amino alcohols such as ethanolamine, isopropanolamine, methylethanolamine or aminoethoxyethanol. It is also possible to use structural components e) which contain more than two functional groups which are reactive toward isocyanate
• proportions of components a) to e) are chosen in particular so that the sum of the functional groups reactive toward isocyanate, i.e. the hydroxyl or primary or secondary amino groups, is 0.8 to 1.2, preferably 0.95 to 1.05 gram equivalents over 1 gram equivalent of isocyanate.
• the number of functional groups reactive toward isocyanate particularly preferably corresponds to the number of isocyanate groups.
• a content of components d) in the polyurethane is not necessary if the proportion of components b) is already high enough to ensure dispersibility.
• the structural components (a) to (e) can be reacted in a low-boiling, water-miscible organic solvent in a known manner, as described, for. B. is also described in DE-A-34 37 918.
• the reaction temperature is preferably 50 to 100 ° C.
• catalysts such as dibutyltin dilaurate, stannous octoate or 1,4-diazabicyclo (2,2,2) octane, can also be used.
• the polyurethane obtained is then dispersed in water and the organic solvent is removed by distillation to the desired extent, generally completely.
• the polyurethane can also be prepared by first preparing a polyurethane prepolymer in the low-boiling water-miscible organic solvent. In particular, at least the structural components (a) and (b) and optionally c) and, if appropriate, portions of the structural components d) and e) are reacted with one another. The polyurethane prepolymer obtained is then dispersed in water. Then the further implementation can take place in particular with the structural components or the remaining proportions of structural components (d) and (e). Then, as already described above, the organic solvent can be removed.
• the solids content of the aqueous polyurethane dispersion obtained is preferably between 20 and 80% by weight, particularly preferably between 30 and 70% by weight.
• the dispersions of the invention can be used to produce coatings, e.g. B. paints or protective paint, or as adhesives, use.
• tackifying resins e.g. Phenol-formaldehyde resins or epoxy resins.
• the coatings or bonds produced with the dispersions are notable in particular for their low water swellability.
• the particle size of the latex particles was determined indirectly via turbidity measurements.
• the turbidity of a dispersion with a solids content of 0.01% relative to dest. Water determined at a layer thickness of 2.5 cm and room temperature.
• the films were then stored in water for 24 hours at room temperature and the water absorption was determined by the weight gain.
• the solvent was distilled off at 80 mbar and 40 ° C.
• the solvent was distilled at 84 mbar and 40 ° C.
• the solvent was distilled off at 90 mbar and 40 ° C.
• the solvent was distilled off at 88 mbar and 40 ° C.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Polyurethanes Or Polyureas (AREA)
• Adhesives Or Adhesive Processes (AREA)

Applications Claiming Priority (2)

Publications (3)

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ID=6446582

Family Applications (1)

Country Status (7)

Cited By (5)

Families Citing this family (17)

Citations (3)

Family Cites Families (5)

• 1991
  • 1991-12-09 DE DE4140486A patent/DE4140486A1/de not_active Withdrawn
• 1992
  • 1992-11-20 JP JP4311883A patent/JPH07165860A/ja not_active Withdrawn
  • 1992-11-25 ES ES92120002T patent/ES2086620T3/es not_active Expired - Lifetime
  • 1992-11-25 EP EP92120002A patent/EP0546375B1/fr not_active Expired - Lifetime
  • 1992-11-25 DE DE59206363T patent/DE59206363D1/de not_active Expired - Lifetime
  • 1992-11-30 CA CA002084179A patent/CA2084179A1/fr not_active Abandoned
  • 1992-12-08 AU AU30027/92A patent/AU3002792A/en not_active Abandoned
  • 1992-12-09 US US07/987,602 patent/US5342915A/en not_active Expired - Lifetime

Patent Citations (3)

Non-Patent Citations (2)

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